Preparation of mercaptans



' adsorbent material.

Patented Dec. 15, .1931 I our-ran STATES PATENT OFFICE ERNST u. .romnsmw, or rnmammrma, ranumvanm, assrenoa 'ro m GRAY PROCESSES CORPORATION, or

AWARE rammnarron or Hummus in Drawing.

This invention relates to a rocess for pro- 'ducing sulphur compounds ii'om" hydrocarbons, more particularly to the production of sulphur compounds having the characteristic properties or mercaptans, from unsaturated hydrocarbons contained in or derived from petroleum or natural ga's,or other slmilar mineral source. I This application is a continuation in part of my filed June 22, 1926.

differentiated from covered by the claims in such prior. application, in that a solid adsorbent material, as

for example, fullers earth, or the equivalent is used as a catalyst instead of a mineral acid.

I have found that the sulphur compounds of the character of mercaptans are produced by causing unsaturated hydrocarbons and hydrogen sulfide to react at temperatures of from 32 F. to 100 F., in the presence of catalysts of the solid adsorbent type, such as fullers earth, charcoal, silica gel or the equivalent.

In accordance with this invention, unsaturated hydrocarbons, preferably those contained in a liquid fraction from petroleum, are cause to react with hydrogen sulfide at ordinary temperatures, as for example of the order of from 32 F. to 100 F., preferably by introducing the hydrogen'sulfide into hydrocarbon material comprised at least in part of unsaturated hydrocarbons and thereafter passing the solution of hydrogen sulfite in the hydrocarbon material into contact with solid catalytic material, whereby sulphur derivatives of the hydrocarbon are formed having properties characteristic of the mercaptans. The introduction of 'hydogen sulfide into the hydrocarbon is continued for some period of time, such period being determined by the speed with which the frac: tion takes up the gas or until sufiicient of the gas has been dissolved in the fraction to react therewith to the extent-desired. The resulting solution is then contacted with the If desired, these steps may be repeated anumber of times to efi'ect com ete reaction, which is evidenced b no furt er reaction taking place upon repetltion prlor application Serial No. 117,866,... The present invention is the invention specifically Applicat'imi flled August- 1a, 1929. Serial No. 385,899.

thereof. In each instance the treated solution is separated from the adsorbent materiefiigefore further treatment with hydrogen su e.

The hydrocarbon fraction after saturation with hydrogen sulfide, ifdesired, may be filtered through a bed of the adsorbent material, thereby to cause the reaction to take place and in effect making the process continuous.

It is, however, to be understood that the above is the preferred method and that my invention comprehends broadly the step of causing hydrogen sulfide to react with unsaturated hydrocarbons in the presence of a catalyst of the class described.

After the reaction between the hydrogen sulfide and the unsaturated hydrocarbons has been completed, the resulting solution may be subjected to distillation and re-distillation to eliminate any non-volatile substances present, and the distillate comprisinga solution of the. sulphur compounds results, which distillate I have found possesses characteristic mercaptan reactions.

The natureof the reaction between the unsaturated hydrocarbons and the hydrogen sulfide may be a direct addition of the gas to the hydrocarbons and ma the formation of ethy -mercaptan from ethylene and hydrogen sulfide accordingto the following equat1on, which maybe considered as typical of that which'takes place between hydrogen sulfide and any of the unsaturated hydrocarbons:

As a more specific example of the present be illustrated by NEWARK, NIEHF JERSEY, A CORPORATION Q1 DED- process, a liquid hydrocarbon fraction from a petroleum distillate, 9% by volume of which will react with sulphuric acid of 95% H 30, content, said fractior. being free of mercaptans, and having a boiling range ofufrom about 114 content of 0.04% is treated by method; as above described with hydrogen sulfide, then agitated with granular fullers weight of fullers earth to 60 parts by weig t of the earth in the proportion of 20 parts b solution, until the hydrogen sulfide odor has substantially disappeared. The liquid is th en to about 4143'F., and a sulphur the preferred fullers earth, chamoa], and silica. gel, sepmating the liquid from the adsorbent and the liquid with dilute alkali metal hydroxide.

5. A process for producing compounds which comprises intmduqmg hydrogen sulfide into a liquid oontaimug o the solution into contact w1 th a solid adsorbent from the group of fulleflseumdnmoahmdsilicagegm betweenafi Faudlofl F the liquid with dilute Ilklll metal hyd mxide.

GMZA process for sulfur oomds whidl comprises brmgmg mutant with by sulfide and en to met at ordinary fempentumes by having s eaflh presenh.

\wTZi m PW h fedan g hydrogen 51 111 with com riw ;"1 v phide and diefins to the aehon of an adsorptiwe cahlyd; oommleofthegmup mmof fullels earth and siheaiel.

8. p for producing sulp ur mum ds which comprises olefii ns m-mctwiihhysulphldemthepmsenoeofasolidadso ltfmmthegmupof fuller senfh, charcoal and silica,

l nyivhueoflafixmy mscr M. JOHANSEN. 

